Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
  • B05D3/101—Pretreatment of polymeric substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
  • B65D25/34—Coverings or external coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/048—Forming gas barrier coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31913—Monoolefin polymer
  • Y10T428/3192—Next to vinyl or vinylidene chloride polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

• the present invention relates to a coated styrene-based resin container and a method for producing the same, and more specifically, it is not necessary to provide a special anchor layer on a styrene-based resin container.
• the present invention relates to a container provided with a coating of a vinylidene chloride resin having excellent adhesion when wet, and a method for producing the same.
• Aqueous latex of vinylidene chloride resin is widely used to form a coating layer on various packaging materials because it can form a coating with excellent gas permeability to various gases such as oxygen and water vapor. It is also used, for example, for coating the inner or outer surface of biaxially stretched polyester containers.
• styrene resin containers are widely used as easy packaging containers because they are inexpensive and easy to mold, but styrene resins have the highest gas permeability. It is one of the large resins, and there is a problem in the preservation of the contents, and its improvement is desired. '
• U.S. Pat. No. 3,328,6 discloses that a polymer or copolymer of alkyl methacrylate is provided as an anchor coat layer on a stretched molded article of styrene, and the anchor coat layer is formed on the stretched molded article. It describes that a latex of vinylidene chloride-based resin is applied on the coating layer.
• an object of the present invention is to provide a coated styrene resin container in which a styrene resin container main body and a coating layer of vinylidene chloride resin are firmly adhered without an anchor coat layer.
• the container comprises: a container body made of a styrene resin; and a vinylidene chloride resin coat layer applied to at least one surface of the container.
• the coating layer of the dendritic resin is composed of 96 to 70% of vinylidene chloride units, 3 to 30% of vinyl chloride units, and lower alkyl ester of acrylic acid or methacrylic acid, based on the molar ratio of the three components.
• Len-based resin containers can be provided.
• At least one surface of the container body composed of a styrene resin has an area ratio of oxygen beak per carbon beak of 0, 15 measured by X-ray photoelectron spectroscopy.
• vinylidene chloride level of 96 to 70%, vinyl chloride unit of 3 to 30%, and acrylic acid or mesylate on a three-component molar basis.
• An aqueous latex of vinylidene chloride tea resin containing 3 to 20% of lower alkyl ester of acrylic acid is applied to the oxidized surface of the container body to form a coating layer.
• a method for producing a coated styrene-based resin container characterized by drying is provided.
• FIG. 1 is a sectional view showing the structure of a container according to the present invention.
• Fig. 2 shows the XPS spectrum of the surface of a styrene-based resin container that has not been oxidized.
• Fig. 3 shows an XPS spectrum of a styrene-based resin container that has been oxidized. .
• FIG. 4 is an explanatory view of a test method of the peel strength of the coating film of the sample.
• FIG. 5 is an explanatory view of a method for testing the bending resistance of a coating film of a sample.
• this container 1 comprises a container body 2 made of a styrene resin and a coating layer 3 of a vinylidene chloride resin.
• the coating layer 3 is firmly adhered through the styrene resin oxide layer 4 formed on the surface of the container body.
• the present invention is characterized by forming an oxide layer of styrene tea resin on the surface of the container body and selecting a vinylidene chloride resin having a specific composition described below. It is possible to apply a vinylidene chloride-based resin latex to a styrene-based resin container without the need for an anchor coat layer, and the separation resistance between the coating layer and the container body, especially during low-temperature wetness Is significantly improved.
• the composition of the vinylidene chloride resin constituting the latex is 98 to 60%, especially 96 to 70%, of vinylidene chloride units on a molar basis of three components.
• the vinylidene chloride level governs the gas permeability of the coating, while the vinyl chloride level of the copolymer component is the glass transition point (TS) of the resin.
• TS glass transition point
• the lower alkyl ester of acrylic acid or methacrylic acid enhances the adhesion between the coating and the styrenic resin substrate. It will improve it.
• the vinylidene chloride tea resin having the above composition in the form of a latex excellent coating properties (film-forming properties) and adhesion to the styrene-based resin container body can be obtained. It will be.
• the molar ratio of each unit of the vinylidene chloride resin used is within the above range, and when the amount of vinylidene chloride is less than the above range, the gas barrier against oxygen, steam, etc.
• the resilience is significantly reduced compared to when it is within the above range, and more than the above range In this case, the tendency to lower the film forming property and the adhesion of the coating at a low temperature is increased, and neither is preferable.
• the amount of vinyl chloride is less than the above range, the film forming property at low temperature tends to be slightly reduced and the coating tends to be brittle, while when the amount is more than the above range, the gas resistance is low. Not good in terms of permeability.
• the amount of the ester group of acrylic acid or methacrylic acid is smaller than the above range, the adhesiveness of the coating tends to decrease remarkably.
• the resistance is also high. It is not preferred in terms of gas permeability.
• styrene or a certain resin constituting the container body is a thermoplastic resin mainly composed of styrene, and examples thereof include a styrene homopolymer and a copolymer.
• the hugely particularly suitable styrene resin of the present invention is 99 to 60 mol%, especially 99 to 70 mol% of styrene, and 1 to 40 mol%, especially 1 to 30 mol%.
• Butadiene and a styrene-butadiene copolymer is particularly suitable for the present invention because the surface oxide layer can be easily formed compared to other styrene resins.
• the container body by forming the container body with the styrene-butadiene copolymer, it is possible to improve the impact resistance of the container itself, especially at low temperatures.
• ordinary polystyrene can be used, or a blend of polystyrene and polybutadiene or styrene-butadiene rubber can be used. Can also be used.
• a blend of polystyrene and the above-mentioned styrene-butadiene copolymer can be used.
• the molecular weight of the styrene resin used is generally in the range of 1 ⁇ 10 to 1 ⁇ 10 6 , and particularly preferably in the range of 2 ⁇ 10 4 to 5 ⁇ 10 5 .
• a compounding agent known per se for example, pigments such as titanium white, yellow iron oxide, red iron oxide, pertramaline blue, iron black, etc .
• Fillers such as silica, talc, magnesium hydroxide, and aluminum hydroxide; antioxidants, ultraviolet absorbers, lubricants, etc. can be added.
• the container body may be of any shape, such as a seamless cup, tray, bottle, can, or the like, and the container wall may be substantially oriented in a uniaxial or biaxial direction. It may be one having a molecular orientation. Further, the container wall may be formed of a non-foamed styrene-based resin, may be formed of a foamed styrene-based resin, or may be a combination thereof.
• the container body is molded according to the shape of the container, using a molding method known per se, for example, extrusion molding, injection molding, blow molding, vacuum molding, air pressure molding, plug assist molding, biaxial stretching blow molding, or foaming beads. It is performed by any means such as foam molding.
• the oxide layer formed on the surface of the styrene resin container is obtained by oxidizing the styrene resin itself.
• the thickness of this oxide layer is between 1 and 1000 ⁇ ngström (person).
• XPS X-ray photoelectron spectroscopy
• the binding energy at which the IS beak appears depends on the bonding mode between oxygen and carbon, for example,
• the binding energy is about 532 to 533.7 & V, especially about 532.5 to If an oxide layer having a peak of 0 IS at 533.6 eV is formed, satisfactory results can be obtained with respect to the coating property of the latex and the adhesion of the coating. Special attention should be paid to 0! When the binding energy at which the s peak appears exceeds 533.6 eV, the adhesion to the coating is rather reduced. This is presumably because the ratio of the bond of the above formula (1) in the bond between oxygen and carbon is increased, and the physical properties of the oxide layer itself are weakened.
• the surface ratio of the oxygen peak (0 [ s] ) corresponding to the carbon beak (c IS ) measured by the X-ray photoelectron spectroscopy described above was measured on the surface of the container body (R o / c).
• the oxidation treatment is preferably carried out so as to be in the range of 0.1 to 0.34, particularly 0.15 to 0.32. This R. If / c is lower than the above range, the effect of improving applicability and adhesion is not sufficient, and if / c is higher than the above range, adhesion, particularly peeling resistance at the time of low-temperature wetting is reduced. It will be.
• the container body may be oxidized by a method known per se, for example, a method of oxidizing the surface of a molded container by contacting with a gas ⁇ , a method of oxidizing by contacting with heated air, or an oxidizing method by contacting with a mixed solution of sulfuric acid and chromic acid.
• the vinylidene chloride resin used in the present invention is obtained by the polymerization described above. It has a body composition, but it contains acrylic acid or
• alkaryl esters of lactic acid examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and the like. Or a combination of two or more.
• the vinylidene chloride-based resin is not limited to the above-mentioned terpolymer, and other than the above-mentioned three components, other copolymers may be used in an amount of up to 20 mol%, especially up to 10 mol%, based on the total amount of the three components.
• Monomer components such as acrylonitrile, methacrylonitrile, styrene, vinyl acetate, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. It should be understood that
• Lattes and liquids having a solid content of 20 to 65% by weight, particularly 35 to & 0% by weight are advantageously used.
• the emulsifier in the latex is not particularly limited, and may be, for example, a sodium dodecylbenzenesulfonate $ ⁇ -gianion tea surfactant.
• Latex is applied by dip coating, roll coating, spray coating, electrostatic coating, brush coating, etc. More done.
• the application conditions are not particularly limited, and it is a remarkable feature that sufficient application and film formation are performed at room temperature by using the above-mentioned vinylidene chloride tea resin.
• the styrene-based resin container can be heated to a temperature of 40 to 6.
• the coating amount of the latex may be such that the thickness after drying becomes Q.5 to 60 m, especially 1 to 30 ⁇ .
• the applied wet coating of vinylidene chloride tea resin is dried to obtain a final coating.
• This drying process can be carried out in one or more stages, for example by irradiating the wet coating with far infrared radiation to raise its temperature to 60 to 90, and then raising it to a hot air at 40 to 10Q. To remove moisture.
• drying can be performed efficiently and in a short time.
• the coated styrene resin container according to the present invention has several features not found in conventional ones. That is, the coating layer of vinylidene chloride tea resin has an excellent gas barrier with an oxygen permeability coefficient at 28 t: 100% RH of 3.0 X 10-13 cc-cra / cni 2 -sec-cfflHg or less. while not possess gender, glass transition Utsuriten relatively low as 6 to 1 8, the dynamic elastic modulus at in or 1 0 2 X 1 0 1 ° to 4 X 1 0 1 ° dyne / cm 2 (110 Hz) and relatively low elastic modulus. Due to this property, this coat layer does not break or crack even when subjected to rough handling at low temperatures, and is free from oxygen and other gases. W hi 88/05409
• this coated container has excellent release resistance, especially when exposed to low-temperature wetness, and has a wet release strength of at least 80 s / 18 mni width when immersed in water for 5 weeks. It has the characteristic that it has a width of 100 mm or more and a width of 18 mm or more.
• the present invention will be described with the following examples. Examples The peel strength of the coating film, the evaluation of the bending resistance, and the measurement of the XPS vector were performed by the following methods. "Coating film evaluation method” i) Measurement of coating film peel strength
• test piece was prepared by cutting the body of a tub-shaped container coated with vinylidene chloride resin on the outer surface.
• Fig. 4 explains the test method for the peel strength of the coating film.
• the reference numerals in the figure indicate the following.
• the wet separation strength shall be measured by the above method immediately after removing the coated container immersed in water for 1 week at 5 :.
• the separation strength during drying shall be measured by the above method for a coating container not immersed in water.
• Fig. 5 1 is a coated styrene-based resin container, 7 is an R 4.5 mm round bar, and 8 is a test jig.
• the body was pressed and deformed with a 09 mm round bar at a speed of 50 mm / rain at a speed of 50 mm / rain. At this time, judgment is made based on whether or not cracking or separation of the coating film has occurred.
• the XPS spectrum was measured at ESCA LAB 5 manufactured by VG, UK, and the MgK ⁇ ray was used as the X-ray source.
• 0 binding energy of IS electronic beaks are those obtained by hydrocarbon portion C IS binding energy of electrons in the beak of (CH) and 285 eV.
• Corona discharge treatment time (sec) XPS spectrum area ratio Ro / c 0 I s peak binding energy (e ⁇ Z)

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Laminated Bodies (AREA)
• Containers Having Bodies Formed In One Piece (AREA)
• Details Of Rigid Or Semi-Rigid Containers (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=11772494

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (12)

Family Cites Families (14)

• 1987
  • 1987-01-22 JP JP1124387A patent/JPS6423937A/ja active Granted
• 1988
  • 1988-01-21 WO PCT/JP1988/000041 patent/WO1988005409A1/ja active IP Right Grant
  • 1988-01-21 EP EP88901094A patent/EP0302938B1/de not_active Expired - Lifetime
  • 1988-01-21 US US07/294,637 patent/US4919985A/en not_active Expired - Fee Related
  • 1988-01-21 AU AU11845/88A patent/AU592487B2/en not_active Ceased
  • 1988-01-21 DE DE3889802T patent/DE3889802T2/de not_active Expired - Fee Related

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events